Organophosphorus compounds and its insecticides acaricides and nematocides containing same

ABSTRACT

Insecticidal, acaricidal or nematocidal compositions which comprise organophosphorus compounds of the formula ##STR1## wherein R 1  and R 2  each represents a C 1  to C 4  alkyl group; 
     X represents NH or N--R 4  wherein R 4  represents an alkyl; an alkenyl; an alkynyl; a phosphoric acid ester radical; a cyano group; a group of formula (II): ##STR2##  (wherein R 5  represents an alkyl or alkylamino group); or a group of the formula: --(R 6 ) n  --CO--R 7  (wherein n is 0 or 1; R 6  represents a methylene or an ethylene group; and R 7  represents an alkyl, an alkoxy, an alkylthio group, an alkylamino group or a hydrogen atom); 
     Z represents N--R 8  (wherein R 8  represents a nitro group, a cyano group, an alkylsulfonyl group, a tosyl group or an alkylcarbonyl group) or a group represented by the formula: C(CN)R 9  (wherein R 9  represents a cyano group or an alkoxycarbonyl group); and 
     A represents an ethylene group which may be substituted with C 1  to C 3  alkyl, 
     excluding organophosphorus compounds of formula (I) in which R 1  and R 2  are C 1  to C 4  alkyl groups, X is NH, Z is a cyanoimino group or a nitroimino group and A is an ethylene group.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an organophosphorus compoundrepresented by the following general formula (I): ##STR3## [wherein R¹and R² each represents a C₁ to C₄ alkyl group; X represents O, S, CH₂,CH--R³ (wherein R³ represents a C₁ to C₃ alkyl group), NH or N--R⁴{wherein R⁴ represents a C₁ to C₄ alkyl group (the alkyl group may besubstituted with at least one group selected from the group consistingof alkoxy, alkylthio, cyano, alkoxyalkyloxy and alkylamino groups andhalogen atoms), an alkenyl group which may be substituted with halogenatoms, an alkynyl group which may be substituted with halogen atoms, aphosphoric acid ester radical, a cyano group, a group of the followinggeneral formula (II): ##STR4## (wherein R⁵ represents an alkyl oralkylamino group which may be substituted with halogen atoms) or a grouprepresented by the following general formula: --(R⁶)_(n) --CO--R⁷(wherein n is 0 or 1; R⁶ represents a methylene group which may besubstituted with alkyl groups, or an ethylene group which may besubstituted with alkyl groups; R⁷ represents an alkyl group which may besubstituted with halogen atoms, an alkoxy group which may be substitutedwith halogen atoms, an alkylthio group, an alkylamino group or ahydrogen atom)}; Z represents a group represented by the generalformula: N--R⁸ (R⁸ represents a nitro group, a cyano group, analkylsulfonyl group which may be substituted with halogen atoms, a tosylgroup or an alkylcarbonyl group which may be substituted with halogenatoms) or a group represented by the general formula: C(CN)R⁹ (whereinR⁹ represents a cyano group or an alkoxycarbonyl group); and Arepresents an ethylene group which may be substituted with C₁ to C₃alkyl groups, a trimethylene group which may be substituted with C₁ toC₃ alkyl groups or a group represented by the general formula: --CH₂NR¹⁰ CH₂ -- (wherein R¹⁰ is a C₁ to C₃ alkyl group)]. The compound offormula (I) according to the present invention specifically excludes anorganophosphorus compound of the general formula (I) in which R¹ and R²are C₁ to C₄ alkyl groups respectively, X is NH, Z is a cyanoimino groupor a nitroimino group and A is an ethylene group which may besubstituted with C₁ to C₃ alkyl groups or a trimethylene group which maybe substituted with C₁ to C₃ alkyl groups. The present invention alsorelates to a method for preparing the compound, of formula (I), andinsecticides, acaricides and nematocides which comprise the compound asan active ingredient.

2. Prior Art Statement

Recently, organophosphorus compounds having an imidazolidinyl group havebeen investigated and developed. For instance, Japanese UnexaminedPatent Publication No. Sho 61-267594 and Japanese Unexamined PatentPublication No. Hei 2-793 disclose that these compounds can be used asinsecticides, acaricides, nematocides and agents for killing soil insectpests. However, these patents simply disclose organophosphorus compoundshaving an imidazolidine skeleton which carries an oxygen or sulfur atomon the 2-position. Moreover, the insecticidal, acaricidal andnematocidal effects of these compounds are insufficient and are notnecessarily satisfactory.

OBJECTS AND SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a novelorganophosphorus compound represented by the foregoing general formula(I).

Another object of the present invention is to provide a method forpreparing a novel organophosphorus compound represented by the foregoinggeneral formula (I).

A further object of the present invention is to provide an agriculturalchemical having insecticidal, acaricidal and nematocidal effects higherthan those attained by conventional agricultural chemicals andexhibiting very low toxicity to warm-blooded animals.

The inventors of this invention have synthesized a variety oforganophosphorus compounds carrying an imidazolidinyl group and haveinvestigated the insecticidal, acaricidal and nematocidal activities ofthe organophosphorus compounds having an imidazolidine skeleton whichcarries a specific substituent on the 2-position in order to developeffective insecticides, acaricides and nematocides. As a result, theinventors have found out that excellent control of harmful insect pestscan be achieved by an organophosphorus compound (hereinafter referred toas "the compound of the present invention") represented by the followinggeneral formula (I): ##STR5## [wherein R¹ and R² each represents a C₁ toC₄ alkyl group; X represents O, S, CH₂, CH--R³ (wherein R³ represents aC₁ to C₃ alkyl group), NH or N--R⁴ {wherein R⁴ represents a C₁ to C₄alkyl group (the alkyl group may be substituted with at least one groupselected from the group consisting of alkoxy, alkylthio, cyano,alkoxyalkyloxy and alkylamino groups and halogen atoms), an alkenylgroup which may be substituted with halogen atoms, an alkynyl groupwhich may be substituted with halogen atoms, a phosphoric acid esterradical, a cyano group, a group of the following general formula (II):##STR6## (wherein R⁵ represents an alkyl or alkylamino group which maybe substituted with halogen atoms) or a group represented by thefollowing general formula: --(R⁶)_(n) --CO--R⁷ (wherein n is 0 or 1; R⁶represents a methylene group which may be substituted with alkyl groups,or an ethylene group which may be substituted with alkyl groups; R⁷represents an alkyl group which may be substituted with halogen atoms,an alkoxy group which may be substituted with halogen atoms, analkylthio group, an alkylamino group or a hydrogen atom)}; Z representsa group represented by the general formula: N--R⁸ (R⁸ represents a nitrogroup, a cyano group, an alkylsulfonyl group which may be substitutedwith halogen atoms, a tosyl group or an alkylcarbonyl group which may besubstituted with halogen atoms) or a group represented by the generalformula: C(CN)R⁹ (wherein R⁹ represents a cyano group or analkoxycarbonyl group); and A represents an ethylene group which may besubstituted with C₁ to C₃ alkyl groups, a trimethylene group which maybe substituted with C₁ to C₃ alkyl groups or a group represented by thegeneral formula: --CH₂ NR¹⁰ CH₂ -- (wherein R¹⁰ is a C₁ to C₃ alkylgroup)]. The compound of formula (I) according to the present inventionspecifically excludes an organophosphorus compound of the generalformula (I) in which R¹ and R² are C₁ to C₄ alkyl groups respectively, Xis NH, Z is a cyanoimino group or a nitroimino group and A is anethylene group which may be substituted with C₁ to C₃ alkyl groups or atrimethylene group which may be substituted with C₁ to C₃ alkyl groups.Thus, the present invention has completed on the basis of the foregoingfinding.

These organophosphorus compounds do not give off any bad or irritatingodor and have low toxicity to warm-blooded animals. Therefore, they canwidely be used and thus have very high usefulness.

The organophosphorus compounds represented by the foregoing generalformula (I) also include stereoisomers such as optical isomers. Inaddition, in the general formula (I), when X is the group NH, theorganophosphorus compounds may exist in the form of a tautomerrepresented by the following general formula (I'): ##STR7## (wherein R¹,R², Z and A are the same as those defined above). These compounds(tautomeric isomers) are likewise included in the scope of the compoundof the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of the present invention can be prepared in accordancewith, for instance, any one of the following three methods. ##STR8##(Wherein R¹, R², R⁴, X, Z and A are the same as those defined above andHal means a halogen atom).

The foregoing reactions are in general carried out at a temperatureranging from -100° to +60° C. and preferably from -80° to +30° C.Moreover, these reactions are performed in the presence of adeacidifying agent, examples of which include organic lithium compoundssuch as n-butyl lithium, t-butyl lithium and phenyl lithium; inorganicbases such as sodium hydride, potassium hydride, metallic sodium, sodiumhydroxide and potassium hydroxide; alkoxides such as sodium methoxide,sodium ethoxide and potassium t-butoxide; and organic bases such astriethylamine and pyridine.

In addition, these reactions are desirably carried out in the presenceof a solvent. Examples of such solvents include aromatic hydrocarbonssuch as benzene, toluene, xylene and chlorobenzene; cyclic or non-cyclicaliphatic hydrocarbons such as hexane and cyclohexane; ethers such asdiethyl ether, methyl ethyl ether, dioxane and tetrahydrofuran; nitrilessuch as acetonitrile, propionitrile and acrylonitrile; and aprotic polarsolvents such as dimethylformamide, dimethylsulfoxide, sulfolane andhexamethyl-phosphoric acid triamide.

Typical examples of the compounds of the present invention will now belisted in the following Table 1. Each compound will hereinafter bedescribed by the corresponding number of the compound. ##STR9##

In the following Table 1, the symbol "←" as set forth in the column"←A-" represents a bond with X and "ph" means a p-phenylene group.

                                      TABLE 1-1                                   __________________________________________________________________________    Comp. No.                                                                           R.sup.1                                                                          R.sup.2                                                                           ←A--                                                                           X     Z        Physical Property                           __________________________________________________________________________    1     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N--CH.sub.3                                                                         N--NO.sub.2                                                                            m.p.: 46.0˜48.0° C.            2     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N--C.sub.2 H.sub.5                                                                  N--NO.sub.2                                                                            oily substance                              3     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N--CH.sub.3                                                                         N-CN     oily substance                              4     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N--C.sub.2 H.sub.5                                                                  N-CN     oily substance                              5     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N-n-C.sub.3 H.sub.7                                                                 N-CN     oily substance                              6     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               N-n-C.sub.4 H.sub.9                                                                 N-CN     oily substance                              7     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               NH    C(CN).sub.2                                                                            oily substance                              8     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               NH    N--SO.sub.2 -ph-4-CH.sub.3                                                             oily substance                              9     C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                 --(CH.sub.2).sub.2 --                                                               NH    N--SO.sub.2 CH.sub.3                                                                   oily substance                              __________________________________________________________________________

                                      TABLE 1-2                                   __________________________________________________________________________    Comp.                                Physical                                 No. R.sup.1                                                                          R.sup.2                                                                            ←A                                                                              X          Z      Property                                 __________________________________________________________________________    10  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     S          NSO.sub.2 CH.sub.3                                                                   oily substance                           11  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     S          NCN    oily substance                           12  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     S          NNO.sub.2                                                                            oily substance                           13  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub.3                                                                     NCH.sub.3  NCN    oily substance                           14  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      ##STR10## NCN    oily substance                           15  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub.2                                                                     NCH(CH.sub.3).sub.2                                                                      NCN    oily substance                           16  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub. 2                                                                    NCH.sub.3  NCN    m.p.: 45.0˜47.0° C.         17  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.3                                                                     NCH.sub.3  C(CN).sub.2                                                                          oily substance                           18  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCH.sub.3  C(CN).sub.2                                                                          oily substance                           19  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCH.sub.3  NSO.sub.2 CH.sub.3                                                                   oily substance                           __________________________________________________________________________

                                      TABLE 1-3                                   __________________________________________________________________________    Comp.                                Physical                                 No. R.sup.1                                                                          R.sup.2                                                                            ←A X         Z      Property                                 __________________________________________________________________________    20  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                 ##STR11##                                                                            NCH.sub.3 C(CN).sub.2                                                                          m.p.: 73.0˜76.0° C.         21  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  CH.sub.2 NCH.sub.2                                                                    NH        NNO.sub.2                                                                            oily substance                           22  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  CH.sub.2 NCH.sub.2                                                                    NCH.sub.3 NNO.sub.2                                                                            oily substance                           23  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  CH.sub.2 NCH.sub.2                                                                    N-n-CH.sub.3 H.sub.7                                                                    NNO.sub.2                                                                            oily substance                           24  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.2 CHCH.sub.2                                                                    NNO.sub.2                                                                            oily substance                           25  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.3 NSO.sub.2 CF.sub.3                                                                   oily substance                           26  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.2 CHCH.sub.2                                                                    NCN    oily substance                           27  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.2 CCH                                                                           NCN    oily substance                           28  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub.2                                                                      NCOCH.sub.3                                                                             NCN    oily substance                           29  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub.2                                                                      NCH.sub.2 OCH.sub.3                                                                     NCN    oily substance                           __________________________________________________________________________

                                      TABLE 1-4                                   __________________________________________________________________________    Comp.                                 Physical                                No. R.sup.1                                                                          R.sup.2                                                                            ←A X        Z        Property                                __________________________________________________________________________    30  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                   ##STR12##                                                                            NCH.sub.2 OC.sub.2 H.sub.5                                                             NCN      oily substance                          31  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                   ##STR13##                                                                            NCH.sub.2 OC.sub.2 H.sub.5                                                             NCN      oily substance                          32  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.9                                                                (CH.sub.2).sub.2                                                                      NSO.sub.2 N(CH.sub.3).sub.2                                                            NCN      oily substance                          33  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.2 SCH.sub.3                                                                    NCN      oily substance                          34  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.3                                                                              NCOCF.sub.3                                                                            oily substance                          35  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NC.sub.2 H.sub.5                                                                       C(CN).sub.2                                                                            oily substance                          36  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      N-n-C.sub.3 H.sub.7                                                                    C(CN).sub.2                                                                            oily substance                          37  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NH       C(CN)COOC.sub.2 H.sub.5                                                                oily substance                          38  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NCH.sub.3                                                                              C(CN)COOC.sub.2 H.sub.5                                                                oily substance                          39  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      NC.sub.2 H.sub.5                                                                       C(CN)COOC.sub.2 H.sub.5                                                                oily substance                          __________________________________________________________________________

                                      TABLE 1-5                                   __________________________________________________________________________    Comp.                                Physical                                 No. R.sup.1                                                                          R.sup.2                                                                            ←A                                                                              X            Z    Property                                 __________________________________________________________________________    40  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                     CH.sub.2     NCN  oily substance                           41  CH.sub.2                                                                         sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                     NCH.sub.3    NCN  m.p.: 76.0˜80.0° C.         42  C.sub.2 H.sub.5                                                                  CH.sub.3                                                                           (CH.sub.2).sub.2                                                                     NCH.sub.3    NCN  m.p.: 116.0˜118.5° C.       43  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                    (CH.sub.2).sub.2                                                                     NCH.sub.3    NCN  oily substance                           44  C.sub.2 H.sub.5                                                                  iso-C.sub.4 H.sub.3                                                                 ##STR14##                                                                           NCH.sub.3    NCN  oily substance                           45  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                CHCH.sub.2                                                                           O            NCN  oily substance                           46  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCOOC.sub.2 H.sub.5                                                                        NCN  oily substance                           47  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCH.sub.2 CN NCN  oily substance                           48  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NSO.sub.2 CH.sub.3                                                                         NCN  oily substance                           49  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                     NCN  oily substance                           50  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                     NCON(CH.sub.3).sub.2                                                                       NCN  oily substance                           __________________________________________________________________________

                                      TABLE 1-6                                   __________________________________________________________________________    Comp.                              Physical                                   No. R.sup.1                                                                          R.sup.2                                                                            ←A                                                                              X          Z    Property                                   __________________________________________________________________________    51  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                     N-n-C.sub.3 H.sub.7                                                                      NCN  oily substance                             52  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     NCH.sub.2 OCH.sub.3                                                                      NNO.sub.2                                                                          oily substance                             53  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                     NCH.sub.2 OCH.sub.3                                                                      C(CN).sub.2                                                                        oily substance                             54  C.sub.2 H.sub.5                                                                  sec-C.sub.4 H.sub.3                                                                (CH.sub.2).sub.2                                                                      ##STR15## C(CN).sub.2                                                                        oily substance                             55  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                      ##STR16## NCN  oily substance                             56  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.3                                                                     NCH.sub.3  NCN  m.p.: 58.5˜61.5° C.           57  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     CH.sub.2   NCN  oily substance                             58  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     CHCH.sub.3 NCN  oily substance                             59  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.2                                                                     CH.sub.2   NNO.sub.2                                                                          oily substance                             60  C.sub.2 H.sub.5                                                                  n-C.sub.3 H.sub.7                                                                  (CH.sub.2).sub.3                                                                     CH.sub.2   NCN  m.p.: 44.0˜47.0° C.           __________________________________________________________________________

                  TABLE 2-1                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        1     IR(KBr): 1251(P=O)cm.sup.-1                                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 C --H.sub.2 --C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.0(s, 3H,                                                        NCH.sub.3), 3.8˜4.5(m, 6H, OCH.sub.2, NCH.sub.2 CH.sub.2 N)       2     IR(neat): 1251(P=O)cm.sup.-1                                                  NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.3),                    2.7˜3.75(m, 4H, SCH.sub.2,                                              NCH.sub.2), 3.8˜4.5(m, 6H, OCH.sub.2, NCH.sub.2 CH.sub.2 N)       3     IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 C --H.sub.2 --C -- H.sub.3), 2.7˜3.2(m, 2H,                   SCH.sub.2), 3.3(s, 3H,                                                        NCH.sub.3), 3.5˜4.5(m, 6H, OCH.sub.2, NCH.sub.2 CH.sub.2          ______________________________________                                              N)                                                                  

                  TABLE 2-2                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        4     IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.3),                  2.7˜3.2(m, 2H, SCH.sub.2),                                              3.5˜4.5(m, 8H, OCH.sub.2, NCH.sub.2 CH.sub.2 N, NCH.sub.2)        5     IR(neat): 2170(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 13H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.2 C                  --H.sub.3), 2.7˜3.2(m, 2H,                                              SCH.sub.2), 3.4˜4.5(m, 8H, OCH.sub.2, NCH.sub.2 CH.sub.2 N,             NCH.sub.2)                                                              6     IR(neat): 2170(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 15H, OCH.sub.2 C              -- .sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.2 C                  --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                                  SCH.sub.2), 3.5˜4.5(m, 8H, SCH.sub.2, NCH.sub.2 CH.sub.2 N,             NCH.sub.2)                                                              ______________________________________                                    

                  TABLE 2-3                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        7     IR(neat): 3232(NH), 2194(C.tbd.N), 1257(P=O)cm.sup.-1                         NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.4˜4.5(m,                                                  6H, OCH.sub.2, NCH.sub.2 CH.sub.2 N), 8.00(bs, 1H, NH)                  8     IR(neat): 3376(NH), 1257(P=O)cm.sup.-1                                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 C --H.sub.2 C --H.sub.3), 2.36(s, 3H, ph-C --H.sub.3),              2.6˜3.1(m, 2H,                                                          SCH.sub.2), 3.4˜4.4(m, 6H, OCH.sub.2, NCH.sub.2 CH.sub.2 N),            7.1˜7.9(m,                                                              5H, NH, benzene)                                                        9     IR(neat): 3370(NH), 1257(P=O)cm.sup.-1                                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C  --H.sub.3), 2.7˜3.2(m, 2H,                   SCH.sub.2), 2.93(s, 3H,                                                       SO.sub.2 CH.sub.3), 3.5˜4.5(m, 6H, OCH.sub.2, NCH.sub.2                 CH.sub.2 N), 7.34                                                             (bs, 1H, NH)                                                            ______________________________________                                    

                  TABLE 2-4                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        10    IR(neat): 1257(P=O)cm.sup.-1                                                  NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.5(m, 4H,                    SCH.sub.2, SC --H.sub.2 CH.sub.2 N),                                          2.99(s, 3H, SO.sub.2 CH.sub.3), 3.9˜4.5(m, 4H, OCH.sub.2,               SCH.sub.2 C --H.sub.2 N)                                                11    IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 C --H.sub.2 C --H.sub.3), 2.7˜4.7(m, 8H, SCH.sub.2,           SCH.sub.2 CH.sub.2 N,                                                         OCH.sub.2)                                                              12    IR(neat): 1251(P=O)cm.sup.-1                                                  NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C  --H.sub.3), 2.7˜3.4(m, 4H,                   SCH.sub.2, SC --H.sub.2 CH.sub.2 N),                                          4.0˜4.6(m, 4H, OCH.sub.2, SCH.sub.2 C --H.sub.2 N)                ______________________________________                                    

                  TABLE 2-5                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        13    IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.2(m, 13H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.2              CH.sub.2 N), 3.1˜4.5(m, 7H,                                             SCH, OCH.sub.2, NC --H.sub.2 CH.sub.2 C --H.sub.2 N), 3.35(s, 3H,             NCH.sub.3)                                                              14    IR(neat): 2182(C.tbd.N), 1266(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.1(m, 16H, OCH.sub.2 C              --H.sub.3,                                                                    OCH.sub.2 --C --H.sub.3, SCH.sub.2 C --H.sub.2 C --H.sub.3,                   SCH.sub.2 C --H.sub.2 C --H.sub.3), 2.6˜3.2                             (m, 4H, SCH.sub.2, SCH.sub.2), 3.9˜4.5(m, 8H, OCH.sub.2,                OCH.sub. 2,                                                                   NCH.sub.2 CH.sub.2 N)                                                   15    IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 17H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3, N--CH(C --H.sub.3).sub.2)          , 3.2˜4.5(m, 7H,                                                        SCH, NCH.sub.2 --CH.sub.2 N, OCH.sub.2), 4.7˜5.2(m, 1H,           ______________________________________                                              NCH)                                                                

                  TABLE 2-6                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        16    IR(neat): 2176(C.tbd.N), 1254(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 3.20˜4.5(m, 7H,             SCH,                                                                          NCH.sub.2 CH.sub.2 N, OCH.sub.2), 3.32(s, 3H, NCH.sub.3)                17    IR(neat): 2200(C.tbd.N), 1263(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.1˜3.7(m, 8H,                    NCH.sub.2 CH.sub.2 CH.sub.2 N,                                                SCH.sub.2), 3.35(s, 3H, NCH.sub.3), 3.9˜4.5(m, 2H,                      OCH.sub.2)                                                              18    IR(neat): 2200(C.tbd.N), 1269(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub. 3), 2.6˜4.5(m, 8H,                   SCH.sub.2, NCH.sub.2 CH.sub.2 N,                                              OCH.sub.2), 3.30(s, 3H, NCH.sub.3)                                      ______________________________________                                    

                  TABLE 2-7                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        19    IR(neat): 1617(C═N)cm.sup.-1                                              NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.6˜4.5(m, 8H,                    SCH.sub.2, NCH.sub.2 CH.sub.2 N,                                              OCH.sub.2), 2.97(s, 3H, SO.sub.2 CH.sub.3), 3.30(s, 3H,                 ______________________________________                                              NCH.sub.3)                                                          

                  TABLE 2-8                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        20    IR(KBr): 2200(C.tbd.N), 1265(P=O)cm.sup.-1                                    NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 3.20˜4.5(m, 7H,             SCH,                                                                          NCH.sub.2 CH.sub.2 N, OCH.sub.2), 3.30(s, 3H, NCH.sub.3)                21    IR(neat): 3274(NH), 1248(P=O)cm.sup.-1                                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.56(s, 3H, NCH.sub.3),                 2.70˜3.20(m, 2H,                                                        SCH.sub.2), 3.9˜4.7(m, 6H, OCH.sub.2, NCH.sub.2 N, NCH.sub.2            N), 9.49                                                                      (bs, 1H, NH)                                                            22    IR(neat): 1248(P=O)cm.sup.-1                                                  NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C -- H.sub.3), 2.58(s, 3H, NCH.sub.3),                3.0(s, 3H, NCH.sub.3),                                                        2.70˜3.2(m, 2H, SCH.sub.2), 3.8˜4.5(m, 6H, NCH.sub.2              N,                                                                            NCH.sub.2 N)                                                            ______________________________________                                    

                  TABLE 2-9                                                       ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        24    IR(neat): 1572(C=N), 1251(P=O)cm.sup.-1                                       NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.7˜4.5(m,                                                  8H, OCH.sub.2, NC --H.sub.2 CH═CH.sub.2, NCH.sub.2 CH.sub.2 N),           5.1˜6.0(m,                                                              3H, NCH.sub.2 C --H═C --H.sub.2)                                    25    IR(neat): 1515(C=N), 1248(P=O)cm.sup.-1                                       NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.13(s, 3H,                                                       NCH.sub.3) 3.6˜4.5(m, 6H, OCH.sub.2, NCH.sub.2 CH.sub.2 N)        26    IR(neat): 2176(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.6˜4.5(m,                                                  8H, OCH.sub.2, NC --H.sub.2 CH═CH.sub.2, NCH.sub.2 CH.sub.2 N),           5.1˜6.0(m,                                                              3H, NCH.sub.2 C --H═C --H.sub.2)                                    ______________________________________                                    

                  TABLE 2-10                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        27    IR(neat): 3232(C.tbd.CH), 2182(C.tbd.N), 1257(P=O)cm.sup.-1                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.38(t, 1H, CH.sub.2 CH.tbd.C           --H), 2.7˜3.2                                                           (m, 2H, SCH.sub.2), 3.6˜4.5(m, 6H, OCH.sub.2, NCH.sub.2                 CH.sub.2 N),                                                                  5.55(d, 2H, NC --H.sub.2 C.tbd.CH)                                      28    IR(neat): 2188(C.tbd.N), 1737(C=O), 1257(P=O)cm.sup.-1                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 2.54(s, 3H, COC                   --H.sub.3), 3.2˜4.7                                                     (m, 7H, SCH, NCH.sub.2 CH.sub.2 N, OCH.sub.2)                           29    IR(neat): 2182(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 3.2˜4.5(m, 7H,              SCH,                                                                          NCH.sub.2 CH.sub.2 N, OCH.sub.2), 3.41(s, 3H, CH.sub.3 O), 5.11(s,            2H,                                                                           NCH.sub.2 O)                                                            ______________________________________                                    

                  TABLE 2-11                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        30    IR(neat): 2182(C.tbd.N), 1260(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 14H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, OCH.sub.2 C --H.sub.3, NCH(C             --.sub.3)CH.sub.2 N),                                                         2.7˜4.5(m, 9H, SCH.sub.2, OCH.sub.2, OCH.sub.2,                         NC --H(CH.sub.3)C --H.sub.2 N),                                               5.14(s, 2H, NCH.sub.2 O)                                                31    IR(neat): 2176(C.tbd.N), 1272(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 17H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, OCH.sub.2 C --H.sub.3,                   NCH.sub.2 C(C --H.sub.3).sub.2 CH.sub.2 N),                                   2.6˜4.5(m, 10H, SCH.sub.2, OCH.sub.2, OCH.sub.2,                        NC --H.sub.2 C(CH.sub.3).sub.2 C --H.sub.2 N), 5.16(s, 2H,                    NCH.sub.2 O)                                                            32    IR(neat): 2188(C.tbd.N), 1263(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 2.95(s, 6H, SO.sub.2              N(CH.sub.3).sub.2),                                                           3.2˜4.5(m, 7H, SCH, NCH.sub.2 CH.sub.2 N, OCH.sub.2)              ______________________________________                                    

                  TABLE 2-12                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        33    IR(neat): 2176(C.tbd.N), 1266(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.25(s, 3H, SCH.sub.3),                 2.7˜3.2(m, 2H,                                                          SCH.sub.2), 3.6˜4.5(m, 6H, NCH.sub.2 CH.sub.2 N, OCH.sub.2),            4.90(s, 2H,                                                                   SCH.sub.2 N)                                                            34    IR(neat): 1662(C=N), 1599(C=N), 1257(P=O)cm.sup.-1                            NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.6˜3.2(m, 2H,                    SCH.sub.2), 2.91(s, 3H,                                                       NCH.sub.3), 3.6˜4.5(m, 6H, NCH.sub.2 CH.sub.2 N, OCH.sub.2)       35    IR(neat): 2200(C.tbd.N), 1263(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.3),                  2.6˜3.2(m, 2H, SCH.sub.2),                                              3.5˜4.5(M, 8H, NCH.sub.2, NCH.sub.2 CH.sub.2 N,                   ______________________________________                                              OCH.sub.2)                                                          

                  TABLE 2-13                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        36    IR(neat): 2200(C.tbd.N), 1265(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 13H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.2 C                  --H.sub.3), 2.6˜3.2(m, 2H,                                              SCH.sub.2), 3.5˜4.5(m, 8H, NCH.sub.2, NCH.sub.2 CH.sub.2 N,             OCH.sub.2)                                                              37    IR(neat): 3292(NH), 2200(C.tbd.N), 1671(C=O),                                 1254(P=O)cm.sup.-1                                                            NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, COOCH.sub.2 C --H.sub.3),                2.6˜3.2(m, 2H, SCH.sub.2),                                              3.5˜4.5(m, 8H, NCH.sub.2 CH.sub.2 N, COOC --H.sub.2 CH.sub.3,           OCH.sub.2),                                                                   9.43(bs, 1H, NH)                                                        38    IR(neat): 2188(C.tbd.N), 1686(C=O), 1257(P=O)cm.sup. -1                       NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, COOCH.sub.2 C --H.sub.3),                2.6˜3.2(m, 2H, SCH.sub.2),                                              3.15(s, 3H, NCH.sub.3), 3.4˜4.5(m, 8H, NCH.sub.2 CH.sub.2 N,            COOC --H.sub.2 --CH.sub.3, OCH.sub.2)                                   ______________________________________                                    

                  TABLE 2-14                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        39    IR(neat): 2188(CN), 1686(CO),                                                 1257(PO)cm.sup.-1 NMR(CDCl.sub.3), δ(ppm):                              0.8˜2.0(m, 14H, OCH.sub.2 C --H.sub.3,                                  SCH.sub.2 C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.3,                     COOCH.sub.2 C --H.sub.3), 2.6˜3.2(m, 2H, SCH.sub.2),                    3.4˜4.5(m, 10H, NCH.sub.2 CH.sub.2 N, NCH.sub.2,                        COOC --H.sub.2 CH.sub.3, OCH.sub.2)                                     40    IR(neat): 2188(CN), 1608(CN),                                                 1254(PO)cm.sup.-1 NMR(CDCl.sub.3), δ(ppm):                              0.8˜2.3(m, 13H, OCH.sub.2 C --H.sub.3, SCH                               ##STR17##                                                              41    IR(KBr): 2176(CN), 1254(PO)cm.sup.-1                                          NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H,                           SCH(C --H.sub.3)                                                              C --H.sub.3 C --H.sub.3),                                                     3.32(s, 3H, NCH.sub.3), 3.2˜3.9(m, 5H, SCH, NCH.sub.2                   CH.sub.2 N),                                                                  3.81(d, 3H, OCH.sub.3)                                                  ______________________________________                                    

                  TABLE 2-15                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        42    IR(KBr): 2176(C.tbd.N), 1254(P=O)cm.sup.-1                                    NMR(CDCl.sub.3), δ(ppm): 1.35(t, 3H, OCH.sub.2 C --H.sub.3),            2.40(d,                                                                       3H, SCH.sub.3), 3.32(s, 3H, NCH.sub.3), 3.6˜4.5(m, 6H, N--              CH.sub.2 CH.sub.2 N, OCH.sub.2)                                         43    IR(neat): 2176(C.tbd.N), 1254(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 1.35(t, 6H, OCH.sub.2 C --H.sub.3,             SCH.sub.2 C --H.sub.3), 2.6˜3.2(m, 2H, SCH.sub.2), 3.32(s,              3H, NCH.sub.3),                                                               3.6˜4.5(m, 6H, NCH.sub.2 CH.sub.2 N, OCH.sub.2)                   44    IR(neat): 2176(C.tbd.N), 1260(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.9˜2.1(m, 10H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 -- --CH(C --H.sub.3).sub.2), 2.7˜3.1(m, 2H,                   SCH.sub.2), 3.32(s, 3H,                                                       NCH.sub.3), 3.6˜4.5(m, 6H, NCH.sub.2 CH.sub.2 N,                  ______________________________________                                              OCH.sub.2)                                                          

                  TABLE 2-16                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        45    IR(neat): 2212(C.tbd.N), 1260(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 14H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3, OC  .sub.--H(C --H.sub.3)          CH.sub.2 N),                                                                  3.2˜4.5(m, 5H, SCH, OCH(CH.sub.3)C --H.sub.2 N, OCH.sub.2),             4.8˜5.4(m, 1H, OC --H(CH.sub.3)CH.sub.2 N)                        46    IR(neat): 2194(C.tbd.N), 1764(C=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3, COOCH.sub.2 C --H.sub.3),                2.72˜3.26(m, 2H,                                                        SCH.sub.2), 3.8˜4.5(m, 8H, NCH.sub.2 CH.sub.2 N, OCH.sub.2,             COOC --H.sub.2 CH.sub.3)                                                47    IR(neat): 2182(C.tbd.N), 1260(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.70˜3.22(m, 2H,                  SCH.sub.2), 3.6˜4.5                                                     (m, 6H, NCH.sub.2 CH.sub.2 N, OCH.sub.2), 4.62(s, 2H, NCH.sub.2         ______________________________________                                              CN)                                                                 

                  TABLE 2-17                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        48    IR(neat): 2188(C.tbd.N), 1260(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.6˜3.2(m, 2H,                    SCH.sub.2), 3.45(s, 3H,                                                       SO.sub.2 CH.sub.3) 3.6˜4.5(m, 6H, NCH.sub.2 CH.sub.2 N,                 OCH.sub.2)                                                              49    IR(neat): 2182(C.tbd.N), 1257(P=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜3.2(m, 2H,                    SCH.sub.2), 3.35(s, 3H,                                                       OCH.sub.3), 3.4˜4.5(m, 10H, NCH.sub.2 CH.sub.2 N, OCH.sub.2             CH.sub.2 O,                                                                   OC --H.sub.2 CH.sub.3), 5.20(s, 2H, OCH.sub.2 N)                        ______________________________________                                    

                  TABLE 2-18                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        50    IR(neat): 2182(C.tbd.N), 1710(C=O)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 3.05 (s, 6H,                      N(CH.sub.3).sub.2), 3.2˜4.5                                             (m, 7H, SCH, NCH.sub.2 CH.sub.2 N, OCH.sub.2)                           51    IR(neat): 2176(C.tbd.N), 1253(P=O).sup.-1                                     NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 16H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3, NCH.sub.2 C --H.sub.2 C            --H.sub.3), 3.2˜4.5(m, 9H,                                              SCH, NCH.sub.2 CH.sub.2 N, NCH.sub.2, OCH.sub.2)                        52    IR(neat): 1563(C=B), 1248(P=O)cm.sup.-1                                       NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 2.7˜4.5(m, 8H,                    SCH.sub.2, NCH.sub.2 CH.sub.2 N,                                              OCH.sub.2), 3.32(s, 3H, OCH.sub.3), 4.70(s, 2H, OCH.sub.2 N)            ______________________________________                                    

                  TABLE 2-19                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        53    IR(neat): 2206(C.tbd.N), 1560(C=C)cm.sup.-1                                   NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 11H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3), 3.2˜4.5(m, 7H,              SCH,                                                                          NCH.sub.2 CH.sub.2 N, OCH.sub.2), 3.39(s, 3H, OCH.sub.3), 5.01(s,             2H,                                                                           OCH.sub.2 N)                                                            54    IR(neat): 2212(C.tbd.N), 1719(C=O), 1563(C=C)cm.sup.-1                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 17H, OCH.sub.2 C              --H.sub.3,                                                                    SCH--(C --H.sub.3)C --H.sub.2 C --H.sub.3, NCOC(CH.sub.3).sub.2),             3.2˜3.8(m, 3H,                                                          SCH, CH.sub.2 Cl), 4.0˜4.5(m, 6H, OCH.sub.2, NCH.sub.2                  CH.sub.2 N)                                                             55    IR(neat): 2176(C.tbd.N), 1722(C=O), 1617(C=N)cm.sup.-1                        NMR(CDCl.sub.3), δ(ppm): 0.8˜2.0(m, 8H, OCH.sub.2 C               --H.sub.3,                                                                    SCH.sub.2 --C --H.sub.2 C --H.sub.3), 1.21(s, 9H,                             C(CH.sub.3).sub.3), 2.7˜4.8(m, 10H,                                     OCH.sub.2, SCH.sub.2, NCH.sub.2 CH.sub.2 N, NCH.sub.2 CO)               ______________________________________                                    

                  TABLE 2-20                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        56    IR(neat): 2170(CN), 1590(CN)                                                  cm.sup.-1 NMR(CDCl.sub.3), δ(ppm): 0.8˜2.2(m, 10H,                OCH.sub.2                                                                     C --H.sub.3, SCH.sub.2 C --H.sub.2 C --H.sub.3,                               NCH.sub.2 C --H.sub.2 CH.sub.2 N), 2.6˜4.5(m, 8H,                       SCH.sub.2),                                                                   OCH.sub.2, NC --H.sub.2 CH.sub.2 C --N), 3.37(s, 3H, NCH.sub.3)         57    IR(neat): 2188(CN), 1608(CN),                                                 1257(PO)cm.sup.-1 NMR(CDCl.sub.3), δ(ppm):                              0.8˜2.4(m, 10H, OCH.sub.2 C --H.sub.3, SCH                               ##STR18##                                                              58    IR(neat): 2188(CN), 1605(CN),                                                 1257(PO)cm.sup.-1 NMR(CDCl.sub.3), δ(ppm):                              0.8˜3.4(m, 16H, OCH.sub.2 C --H.sub.3 SCH.sub.2                          ##STR19##                                                              ______________________________________                                    

                  TABLE 2-21                                                      ______________________________________                                        Comp.                                                                         No.   IR Spectra and NMR Spectra                                              ______________________________________                                        59    IR(neat): 1542(CN), 1263(PO)cm.sup.-1                                         NMR(CDCl.sub.3), δ(ppm): 0.8˜2.4(m, 10H, OCH.sub.2                C --H.sub.3, SCH.sub.2                                                         ##STR20##                                                              60    IR(neat): 2182(CN), 1563(CN),                                                 1254(PO)cm.sup.-1 NMR(CDCl.sub.3), δ(ppm):                              0.8˜2.1(m, 12H, OCH.sub.2 C --H.sub.3,SCH.sub.2                          ##STR21##                                                              ______________________________________                                    

The compounds of the present invention exhibit excellent activity asactive ingredients of insecticides, acaricides and nematocides. Thecompounds of the present invention are effective for controlling, forinstance, agricultural and horticultural pests such as Coleoptera (forinstance, Scarabaeidae, Chrysomelidae, Henosepilachnavigintioctopunctate and Lissorhoptrus oryzophilus), Lepidoptera (forinstance, Mamestra brassicae, Pieris rapae, Plutera xylostella,Noctuidae, Adoxophyes orana and Chilo suppressalis), Hemiptera (forinstance, Delphacidae, Deltocephalidae, Aleyrodidae, Aphididae andScales) and Thysanoptera (for instance, Scirtothrips dorsalis and Thripspulmi); Sanitary pests such as Mosquitoes, Flies, Blattidae, Fleas andLice; Grain pests; cloth and house pests; Plant parasitic nematodes suchas root-knot nematodes and root-lesion nematodes; and Plant parasiticmites such as Tetranychus urticae, Tetranychus cinnabarinus, Tetranychuskanzawai and Panonychus citri. They are also effective for controllingsoil insect pests. The term "soil insect pest" used herein means, forinstance, Gastropoda such as slugs and snails; Isopoda such asArmadillidium vulgare and Sow bugs. In addition, they are likewiseeffective for controlling insect pest such as Dicofol, organophosphoruscompound-resistant plant parasitic mites, organophosphoruscompound-resistant Aphididae and Musca domestica.

When the compounds of the present invention are used as activeingredients of insecticidal, acaricidal, nematocidal compositions andcomposition for killing or controlling soil pest insect, they may beused as such, but may in general be formed into a variety offormulations together with adjuvants such as emulsifiable concentrates,dusts, wettable powders, liquid formulations, aerosols and pastes likeconventional formulations of agricultural chemicals. The formulations ingeneral comprise 0.5 to 90 parts by weight of the active ingredient and10 to 99.5 parts by weight of an adjuvant. When these formulations arepractically used, they can be applied as such or after diluting themwith a diluent such as water to a desired concentration.

The term "adjuvant" herein means carriers, emulsifying agents,suspending agents, dispersing agents, spreaders, penetrants, wettingagents, thickeners and stabilizers. These adjuvants may, if necessary,be added in an appropriate amount. The carriers can roughly beclassified into solid carriers and liquid carriers. Examples of thesolid carriers include vegetable and animal powder such as starches,active carbon, soybean flour, wheat flour, wood powder, fish meal andpowdered milk; and mineral powders such as talc, kaolin, bentonite,calcium carbonate, zeolite, diatomaceous earth, white carbon, clay,alumina and powdered sulfur. On the other hand, examples of the liquidcarriers are water; alcohols such as methyl alcohol and ethylene glycol;ketones such as acetone and methyl ethyl ketone; ethers such as dioxaneand tetrahydrofuran; aliphatic hydrocarbons such as kerosine; aromatichydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene,cyclohexane and solvent naphtha; halogenated hydrocarbons such aschloroform and chlorobenzene; amides such as dimethylformamide; esterssuch as ethyl acetate and glycerin esters of fatty acids; nitriles suchas acetonitrile; and sulfur atom-containing compounds such asdimethylsulfoxide. If necessary, the compounds of the present inventionmay be admixed with or used simultaneously with other agriculturalchemicals such as insecticides, acaricides, nematocides, bactericides,antiviral agents, attractants, herbicides and plant growth regulators.In admixtures, greater effectiveness may sometimes be attained.

Examples of insecticides, acaricides or nematocides includeorganophosphorus acid ester compounds such as DDVP, Diazinon, Malathion,Fenitrothion, Prothiofos, Dioxabenzofos and Acephate; carbamatecompounds such as Carbaryl, Propoxur, Oxamyl, Carbofuran and Methomyl;organochlorine compounds such as Dicofol and Tetradifon; organometalcompounds such as Cyhexatin and Fenbutatin oxide; pyrethroid compoundssuch as Fenvalerate, Permethrin, Deltamethrin and Bifenthrin; ureacompounds such as Diflubenzuron, Teflubenzuron and Chlorfluazuron;heterocyclic compounds such as Buprofezin and Hexythiazox; and othercompounds such as dinitro compounds, organosulfur compounds, amidinecompounds and triazine compounds. In addition to the foregoingcompounds, the compound of the present invention can also be admixedwith or used simultaneously with microbial pesticides such as BT agentsand insect pathogen virus pesticides.

Examples of the bactericides are organophosphorus compounds such asIprobenfos, Edifenphos and Phosethyl-aluminum; organocopper compoundssuch as oxyguinoline copper, copper terephthalate; organochlorinecompounds such as Fthalide and Chlorothalonil; dithiocarbamate compoundssuch as Maneb, Zineb and Propineb; dicarboximide compounds such asIprodione, Vinclozolin and Procymidone; azole compounds such asTriadimefon, Bitertanol, Etaconazole, Propiconazole and Penconazole;benzimidazole compounds such as Thiophanate-methyl and Benomyl; carbinolcompounds such as Fenarimol and Flutriafol; benzanilide compounds suchas Mepronil and Flutolanil; phenylamide compounds such as Metalaxyl andOxadixyl; and other compounds such as piperazine compounds, quinoxalinecompounds, morpholine compounds, anthraquinone compounds, sulfenic acidcompounds, crotonic acid compounds, urea compounds and antibiotics.

As has been discussed above, the insecticides, acaricides andnematocides which comprise, as active ingredient, the compounds of thepresent invention are effective for controlling a variety of deleteriousinsects, harmful mites, destructive nematodes and harmful soil insectpests. These agricultural chemicals or formulations are applied at aconcentration ranging from 1 to 20,000 ppm, desirably 20 to 2,000 ppmexpressed in terms of the amount of the active ingredient. Theconcentration of these active ingredients can be appropriately adjusteddepending on various factors such as shapes of the formulations,methods, purposes, time and places of application as well as thecondition of infestation of insect pest. For instance, when aquaticinsect pests are to be controlled, the insect pest can be controlled byspraying a solution of the compound having a concentration fallingwithin the range defined above and, therefore, the concentration of theactive ingredient required for controlling the aquatic insect pest islower than that defined above. The amount of the agricultural chemicalsor formulations to be applied per unit area (per 10 a) ranges from about0.1 to 5,000 g and preferably 10 to 1,000 g expressed in terms of theamount of the active ingredient, but in a particular case, they may beapplied in an amount outside the range defined above.

The application of a variety of formulations or dilute solutions thereofwhich comprise the compounds of the present invention can be performedaccording to any manner of application usually adopted, for instance,spraying (such as spraying, dusting, misting, atomizing, granuleapplication and application on water surface); soil applications (suchas mixing and drench); surface applications (such as coating, dressingand painting); and poison bait. It is also possible to control thedevelopment and growth of harmful insect pests, in particular deletriousinsects through the action of excreta obtained by admixing the foregoingactive ingredient to feed and giving the feed to domestic animals.Further, they can also be applied in accordance with ultra low volumeapplication. In this method, the chemicals or formulations can comprise100% active ingredient.

EXAMPLES

The method for preparing the compounds of the present invention willhereinafter be explained in more detail with reference to the followingPreparation Examples.

PREPARATION EXAMPLE 1O-ethyl-S-n-propyl-(3-ethyl-2-nitroimino-1-imidazolidinyl)phosphonothiolate(Compound No. 2)

2.00 g ofO-ethyl-S-n-propyl-(2-nitroimino-1-imidazolidinyl)phosphonothiolate wasdissolved in 20 ml of N,N-dimethylformamide and then 0.32 g of a 60%sodium hydride was gradually added to the resulting solution.Thereafter, the solution was cooled down to 0° to 5° C. and 1.27 g ofethyl iodide was gradually added thereto dropwise. After the completionof the dropwise addition, the temperature of the solution was slowlybrought back to room temperature and the solution was further stirredfor additional 12 hours to complete the reaction. After the reaction,the solution was poured into ice water and extracted withdichloromethane. The dichloromethane phase was washed with water, driedover anhydrous magnesium sulfate, the dichloromethane was distilled offunder reduced pressure and the residue obtained was purified by silicagel column chromatography (eluent: ethyl acetate) to give 0.50 g ofCompound No. 2 as an oily substance.

PREPARATION EXAMPLE 2O-ethyl-S-n-propyl-(3-methyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate(Compound No. 3)

To a mixture comprising 0.44 g of a 60% sodium hydride and 50 ml ofN,N-dimethylformamide, 1.24 g of 1-methyl-2-cyanoiminoimidazolidine wasgradually added. After the mixture was allowed to stand for a briefperiod, 2.76 g of an 88.2% toluene solution ofO-ethyl-S-n-propylphosphorochloride thiolate was gradually dropwiseadded to the mixture. After the completion of the dropwise addition, thereaction solution was poured into ice water and then extracted withchloroform. The chloroform phase was washed with water, dried overanhydrous magnesium sulfate, the chloroform was distilled off underreduced pressure and the residue obtained was purified by silica gelcolumn chromatography (eluent: chloroform/methanol=97:3) to give 1.50 gof Compound No. 3 as an oily substance.

PREPARATION EXAMPLE 3O-ethyl-S-n-propyl-(2-methanesulfonylimino-1-imidazolidinyl)phosphonothiolate(Compound No. 9)

2.0 g of 2-methanesulfonyliminoimidazolidine was dissolved in 20 ml ofN,N-dimethylformamide. The resulting solution was cooled down to 0° C.and then 1.02 g of a 60% sodium hydride was gradually added. Thereafter,3.00 g of an 88.2% toluene solution ofO-ethyl-S-n-propylphosphorochloride thiolate was gradually dropwiseadded to the solution. After the completion of the dropwise addition,the temperature of the reaction solution was slowly brought back to roomtemperature and further the reaction was continued for additional 12hours. After the reaction, the reaction solution was poured into icewater, neutralized with a 10% hydrochloric acid solution and thenextracted with chloroform. The chloroform phase was washed with water,dried over anhydrous magnesium sulfate, the chloroform was distilled offunder reduced pressure and the residue obtained was purified by silicagel column chromatography (eluent: chloroform/methanol=97:3) to give2.20 g of Compound No. 9 as an oily substance.

PREPARATION EXAMPLE 4O-ethyl-S-sec-butyl-(3-methoxymethyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate(Compound No. 29)

1.50 g ofO-ethyl-S-sec-butyl-(2-cyanoimino-1-imidazolidinyl)phosphonothiolate wasdissolved in 20 ml of tetrahydrofuran. The resulting solution was cooledand maintained at a temperature of ranging from 0° to 5° C. and 0.25 gof a 60% sodium hydride was gradually added to the solution. After 30minutes, 0.50 g of chloromethyl methyl ether was dropwise added thereto.After the completion of the dropwise addition, the temperature of thereaction solution was brought back to room temperature and the solutionwas stirred for additional 3 hours to complete the reaction.

After the reaction, the reaction solution was poured into ice water andthen extracted with ethyl acetate. The ethyl acetate phase was washedwith water, dried over anhydrous magnesium sulfate, the ethyl acetatewas distilled off under reduced pressure and the residue obtained waspurified by silica gel column chromatography (eluent: chloroform) tothus give 1.10 g of Compound No. 29 as an oily substance.

Specific examples of formulations will be described below, but theadjuvants such as carriers and surfactants are by no means limited tothose used in the following examples. In the following specificformulations, the term "part" means "part by weight" unless otherwisespecified.

FORMULATION EXAMPLE 1 Wettable Powder

20 parts of Compound No. 1, 56 parts of acid clay, 15 parts of whitecarbon, 4 parts of calcium lignin sulfonate and 5 parts ofpolyoxyethylene alkylphenyl ether were uniformly mixed and pulverized togive a wettable powder.

FORMULATION EXAMPLE 2 Emulsifiable Concentrate

To 20 parts of Compound No. 2, 75 parts of xylene was added. And then, 5parts of New Calgen ST-20 (available from Takemoto Oil & Fat Co., Ltd.)was added to the resulting solution as an emulsifying agent and then themixture was mixed and dissolved to give an emulsifiable concentrate.

FORMULATION EXAMPLE 3 Granule

5 parts of Compound No. 1, 3 parts of calcium lignin sulfonate, one partof sodium dodecylbenzenesulfonate, 30 parts of bentonite and 61 parts ofclay were sufficiently pulverized and mixed. The mixture was thensufficiently kneaded while adding water, followed by granulation anddrying to thus give a granule.

The insecticidal, acaricidal and nematocidal effects of the compounds ofthe present invention will hereunder be explained with reference to thefollowing Test Examples.

TEST EXAMPLE 1

The emulsifiable concentrate obtained by Formulation Example 2 wasdiluted with water to 500 ppm and 50 ppm and the resulting dilutedemulsions were sprayed on leaves of chinese cabbage. After air-drying,the leaves were introduced into a plastic container having a size of 21cm (height)×13 cm (width)×3 cm (depth), then 10 third instar larvae ofcommon cutworm were put on the leaves. The container was then placed ina thermostated room maintained at 26° C. After 2 days, the number ofsurviving larvae was recorded to obtain the mortality (%) (repeated twotimes). The results thus obtained are summarized in the following Table3.

                  TABLE 3                                                         ______________________________________                                                   Concn. of                                                          Compound No.                                                                             Active Ingredient (ppm)                                                                        Mortality (%)                                     ______________________________________                                         2         500              100                                                           50               0                                                 3         500              100                                                           50               70                                                4         500              100                                                           50               70                                                5         500              100                                                           50               90                                                6         500              100                                                           50              100                                                7         500              100                                                           50              100                                                9         500              100                                                           50               80                                               10         500              100                                                           50               0                                                14         500              100                                                           50              100                                               15         500              100                                                           50               90                                               16         500              100                                                           50               20                                               17         500              100                                                           50               60                                               18         500              100                                                           50              100                                               20         500              100                                                           50               90                                               21         500              100                                                           50               0                                                26         500              100                                                           50               10                                               27         500              100                                                           50               0                                                29         500              100                                                           50               20                                               30         500              100                                                           50              100                                               31         500              100                                                           50               50                                               32         500              100                                                           50               10                                               33         500              100                                                           50               70                                               34         500              100                                                           50              100                                               35         500              100                                                           50               80                                               36         500              100                                                           50               20                                               37         500              100                                                           50               90                                               38         500              100                                                           50               50                                               39         500              100                                                           50               40                                               40         500              100                                                           50               0                                                41         500              100                                                           50              100                                               44         500              100                                                           50               90                                               45         500              100                                                           50               90                                               46         500              100                                                           50              100                                               47         500              100                                                           50               50                                               49         500              100                                                           50               0                                                50         500              100                                                           50               10                                               51         500              100                                                           50               50                                               53         500              100                                                           50               10                                               Comparative                                                                              500              100                                               Compound A  50               10                                               Untreated  --                0                                                ______________________________________                                    

The Comparative Compound A as set forth in Table 3 is a compoundrepresented by the following structural formula and disclosed inJapanese Unexamined Patent Publication No. Sho 61-267594: ##STR22##

TEST EXAMPLE 2

The emulsifiable concentrate obtained by Formulation Example 2 wasdiluted with water to 500 ppm and the seedlings of rice plant wereimmersed therein for 10 seconds. After air-drying, the seedlings whoseroots were wrapped round with absorbent cotton were introduced into atest tube, then 10 second instar larvae of green rice leafhopper wereput into the test tube, the opening thereof was closed with gauze. Thetube was placed in a thermostated room maintained at 26° C. After 2days, the number of surviving larvae was recorded to obtain themortality (%) (repeated two times). The results thus obtained aresummarized in the following Table 4.

                  TABLE 4                                                         ______________________________________                                                   Concn. of                                                          Compound No.                                                                             Active Ingredient (ppm)                                                                        Mortality (%)                                     ______________________________________                                         1         500              100                                                3         500              100                                                4         500              100                                                5         500              100                                                9         500              100                                               10         500              100                                               11         500              100                                               14         500              100                                               15         500              100                                               16         500              100                                               17         500              100                                               18         500              100                                               19         500              100                                               20         500              100                                               21         500              100                                               26         500              100                                               27         500              100                                               28         500              100                                               29         500              100                                               30         500              100                                               31         500              100                                               32         500              100                                               33         500              100                                               34         500              100                                               35         500              100                                               37         500              100                                               38         500              100                                               40         500              100                                               41         500              100                                               44         500              100                                               45         500              100                                               46         500              100                                               47         500              100                                               49         500              100                                               50         500              100                                               51         500              100                                               53         500              100                                               Comparative                                                                              500              100                                               Compound A                                                                    Untreated  --                0                                                ______________________________________                                    

The comparative Compound A as set forth in Table 4 is the same as thatdefined above in connection with Table 3.

TEST EXAMPLE 3

A kidney bean leaf was cut into 3×5 cm². The leaf was put on a filterpaper wetted with water for preventing drying of the leaf and 20 femaleadults of kanzawa spider mite were released on the leaf. After 24 hours,500 ppm and 50 ppm of concentration of active ingredient prepared bydiluting with water the emulsifiable concentrate obtained by FormulationExample 2 were sprayed on the leaf. After air-drying, the mites wereheld in a thermostated room maintained at 26° C. After 24 hours, thenumber of surviving adults were recorded to obtain the mortality (%)(repeated two times). The results thus obtained are summarized in thefollowing Table 5.

                  TABLE 5                                                         ______________________________________                                                   Concn. of                                                          Compound No.                                                                             Active Ingredient (ppm)                                                                        Mortality (%)                                     ______________________________________                                         1         500              100                                                           50               0                                                 2         500              100                                                           50               0                                                 3         500              100                                                           50               80                                                4         500              100                                                           50               20                                                5         500              100                                                           50               40                                                6         500              100                                                           50               50                                                7         500              100                                                           50               90                                                9         500              100                                                           50               60                                               10         500              100                                                           50               70                                               11         500              100                                                           50               80                                               12         500              100                                                           50               0                                                14         500              100                                                           50               80                                               15         500              100                                                           50               10                                               16         500              100                                                           50               0                                                17         500              100                                                           50               30                                               18         500              100                                                           50               90                                               19         500              100                                                           50               0                                                20         500              100                                                           50               0                                                26         500              100                                                           50               30                                               27         500              100                                                           50               20                                               28         500              100                                                           50               30                                               29         500              100                                                           50               50                                               30         500              100                                                           50               20                                               31         500              100                                                           50               10                                               32         500              100                                                           50               0                                                33         500              100                                                           50               0                                                34         500              100                                                           50               20                                               35         500              100                                                           50               10                                               36         500              100                                                           50               10                                               37         500              100                                                           50               50                                               38         500              100                                                           50               20                                               39         500              100                                                           50               0                                                40         500              100                                                           50               10                                               41         500              100                                                           50               80                                               44         500              100                                                           50               10                                               45         500              100                                                           50               10                                               46         500              100                                                           50               20                                               47         500              100                                                           50               20                                               50         500              100                                                           50               0                                                51         500              100                                                           50               10                                               53         500              100                                                           50               0                                                Comparative                                                                              500              100                                               Compound A  50               10                                               Untreated  --                0                                                ______________________________________                                    

The Comparative Compound A is the same as that defined above inconnection with Table 3.

TEST EXAMPLE 4

To a 1/5,000 are pot, soil contaminated with root-knot nematodes waspacked and the soil was admixed with the granules obtained byFormulation Example 3 in an amount of 250 g and 25 g/are expressed interms of the amount of the active ingredient. Two days after thetreatment, seedlings of tomato at 3rd to 4th-leaf stage weretransplanted in the soil. Twenty-five days after the transplantation,the degree of the invasion of root-knot nematodes (root-knot index) wasdetermined (repeated two times).

The root-knot index was evaluated on the basis of the followingevaluation criteria:

    ______________________________________                                        0        no invasion of root-knot nematodes                                   1        slight invasion of root-knot nematodes                               2        medium invasion of root-knot nematodes                               3        severe invasion of root-knot nematodes                               4        very severe invasion of root-knot nematodes                          ______________________________________                                    

The results thus obtained are summarized in the following Table 6.

                  TABLE 6                                                         ______________________________________                                        Compound Amount of Active Ingredient                                          No.      (g/are)           Root-Knot Index                                    ______________________________________                                         1       250               0                                                            25               3                                                   2       250               0                                                            25               2                                                   3       250               0                                                            25               0                                                   4       250               0                                                            25               0                                                   5       250               0                                                            25               1                                                   6       250               0                                                            25               3                                                   7       250               0                                                            25               1                                                   8       250               0                                                            25               2                                                   9       250               0                                                            25               0                                                  10       250               0                                                            25               2                                                  12       250               0                                                            25               3                                                  14       250               0                                                            25               0                                                  15       250               0                                                            25               0                                                  16       250               0                                                            25               1                                                  17       250               0                                                            25               0                                                  18       250               0                                                            25               0                                                  20       250               0                                                            25               0                                                  21       250               0                                                            25               3                                                  25       250               0                                                            25               3                                                  26       250               0                                                            25               0                                                  27       250               0                                                            25               0                                                  29       250               0                                                            25               0                                                  30       250               0                                                            25               0                                                  31       250               0                                                            25               0                                                  33       250               0                                                            25               2                                                  34       250               0                                                            25               0                                                  35       250               0                                                            25               0                                                  36       250               0                                                            25               2                                                  37       250               0                                                            25               0                                                  38       250               0                                                            25               0                                                  39       250               0                                                            25               0                                                  40       250               0                                                            25               0                                                  41       250               0                                                            25               0                                                  43       250               0                                                            25               3                                                  44       250               0                                                            25               0                                                  45       250               0                                                            25               3                                                  47       250               0                                                            25               3                                                  49       250               0                                                            25               2                                                  50       250               0                                                            25               0                                                  51       250               0                                                            25               0                                                  53       250               0                                                            25               0                                                  54       250               0                                                            25               1                                                  Comparative                                                                            250               0                                                  Compound A                                                                              25               2                                                  Comparative                                                                            250               0                                                  Compound B                                                                              25               1                                                  Untreated                                                                              --                4                                                  ______________________________________                                    

The comparative Compound A as set forth in Table 6 is the same as thatdefined above in connection with Table 3 and Comparative Compound B is acompound (oxamyl) represented by the following structural formula:##STR23##

EFFECT OF THE INVENTION

The compounds of the present invention represented by the foregoinggeneral formula (I) exhibit effectiveness in controlling harmfulinsects, mites and nematodes and thus can be used as novel insecticides,acaricides and nematocides which do not give off a bad or irritatingodor and have low toxicity to warm-blooded animals.

We claim:
 1. An organophosphorus compound represented by formula (I)##STR24## wherein R¹ and R² each represent C₁ to C₄ alkyl;X representsNH or N--R⁴, wherein R⁴ represents C₁ to C₄ alkyl; C₁ to C₄ alkylsubstituted with at least one group selected from the group consistingof alkoxy, alkylthio, cyano, alkoxyalkyloxy, alkylamino and halogen;alkenyl; halogen substituted alkenyl; alkynyl; halogen substitutedalkynyl; phosphoric acid ester; cyano; a group of formula II: ##STR25##(wherein R⁵ represents alkyl, halogen substituted alkyl, alkylamino, orhalogen substituted alkylamino); or --(R⁶) _(n) --CO-- R⁷ (wherein n is0 or 1; R⁶ represents methylene, alkyl substituted methylene, ethyleneand alkyl substituted ethylene; and R⁷ represents alkyl, halogensubstituted alkyl, alkoxy, halogen substituted alkoxy, alkylthio,alkylamino or hydrogen); Z represents N--R⁸ (wherein R⁸ representsnitro, cyano, alkylsulfonyl, halogen substituted alkylsulfonyl, tosyl,alkylcarbonyl or halogen substituted alkylcarbonyl); or C(CN)R⁹,(wherein R⁹ is cyano or alkoxycarbonyl); and A represents ethylene or C₁to C₃ alkyl substituted ethylene; excluding an organophosphorus compoundof formula (I) in which R¹ and R² are C₁ to C₄ alkyl, X is NH, Z iscyanoimino or nitroimino, and A is ethylene or C₁ to C₃ alkylsubstituted ethylene.
 2. The organophosphorus compound according toclaim 1 which isO-ethyl-S-n-propyl-(3-methyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 3. The organophosphorus compound according to claim 1which is O-ethyl-S-n-propyl-(3-ethyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 4. The organophosphorus compound according to claim 1which isO-ethyl-S-n-propyl-(2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.5. The organophosphorus compound according to claim 1 which isO-ethyl-S-n-propyl-(2-methansulfonylimino-1-imidazolidinyl)phosphonothiolate.
 6. The organophosphorus compound according to claim 1which is O-ethyl-S-sec-butyl-(3-methyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 7. The organophosphorus compound according to claim 1which isO-ethyl-S-n-propyl-(3-methyl-2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.
 8. The organophosphorus compound according to claim 1which isO-ethyl-S-sec-butyl-(3-methyl-2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.
 9. The organophosphorus compound according to claim 1which isO-ethyl-S-sec-butyl-(3-methoxymethyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 10. The organophosphorus compound according to claim1 which isO-ethyl-S-n-propyl-[2-(2-cyano-2-ethoxycarbonylmethylene)-1-imidazolidinyl]-phosphonothiolate.11. An insecticidal, acaricidal or nematocidal composition comprising acarrier and, as an active ingredient, an organophosphorus compoundrepresented by formula (I) ##STR26## wherein R¹ and R² each represent C₁to C₄ alkyl;X represents NH or N--R⁴, wherein R⁴ represents C₁ to C₄alkyl; C₁ to C₄ alkyl substituted with at least one group selected fromthe group consisting of alkoxy, alkylthio, cyano, alkoxyalkyloxy,alkylamino and halogen; alkenyl; halogen substituted alkenyl; alkynyl;halogen substituted alkynyl; phosphoric acid ester; cyano; a group offormula II: ##STR27## (wherein R⁵ represents alkyl, halogen substitutedalkyl, alkylamino, or halogen substituted alkylamino); or --(R⁶) _(n)--CO-- R⁷ (wherein n is 0 or 1; R⁶ represents methylene, alkylsubstituted methylene, ethylene and alkyl substituted ethylene; and R⁷represents alkyl, halogen substituted alkyl, alkoxy, halogen substitutedalkoxy, alkylthio, alkylamino or hydrogen); Z represents N--R⁸ (whereinR⁸ represents nitro, cyano, alkylsulfonyl, halogen substitutedalkylsulfonyl, tosyl, alkylcarbonyl or halogen substitutedalkylcarbonyl); or C(CN)R⁹, (wherein R⁹ is cyano or alkoxycarbonyl); andA represents ethylene or C₁ to C₃ alkyl substituted ethylene; excludingan organophosphorus compound of formula (I) in which R¹ and R² are C₁ toC₄ alkyl, X is NH, Z is cyanoimino or nitroimino, and A is ethylene orC₁ to C₃ alkyl substituted ethylene.
 12. An insecticidal, acaricidal ornematocidal composition according to claim 11 wherein the activeingredient compound isO-ethyl-S-n-propyl-(3-methyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 13. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-n-propyl-(3-ethyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 14. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-n-propyl-(2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.
 15. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-n-propyl-(2-methansulfonylimino-1-imidazolidinyl)phosphonothiolate.
 16. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-sec-butyl-(3-methyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 17. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-n-propyl-(3-methyl-2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.
 18. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-sec-butyl-(3-methyl-2-dicyanomethylene-1-imidazolidinyl)phosphonothiolate.
 19. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundis O-ethyl-S-sec-butyl-(3-methoxymethyl-2-cyanoimino-1-imidazolidinyl)phosphonothiolate.
 20. An insecticidal, acaricidal or nematocidalcomposition according to claim 11 wherein the active ingredient compoundisO-ethyl-S-n-propyl-[2-(2-cyano-2-ethoxycarbonylmethylene)-1-imidazolidinyl]-phosphonothiolate.